WO2018110594A1 - Liquid-crystal-display-device sealing agent, vertically conducting material, and liquid crystal display device - Google Patents

Abstract

The purpose of the present invention is to provide a liquid-crystal-display-device sealing agent with which it is possible to achieve adhesiveness as well as prevention of moisture permeation in a cured product. The other purpose of the present invention is to provide a vertically conducting material and a liquid crystal display device that are formed by using the liquid-crystal-display-device sealing agent. The present invention is a liquid-crystal-display-device sealing agent that contains a curable resin, a polymerization initiator, and/or a thermosetting agent, wherein the curable resin contains a compound represented by formula (1). In formula (1), R¹ represents a hydrogen atom or a methyl group, R² represents a group represented by formula (2-1), (2-2), or (2-3), Ar represents an arylene group that may be substituted, X represents an open ring structure of a cyclic lactone, n is 0-5 (average value), and Ep represents a structure of epoxy compound origin. In formulas (2-1) to (2-3), * represents bonding positions; in formula (2-2), a is an integer of 1-8; and, in formula (2-3), b is an integer of 1-8, c is an integer of 1-3, and d is an integer of 1-8.

Description

Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element

The present invention relates to a sealant for a liquid crystal display element that can achieve both adhesiveness and moisture permeation prevention properties of a cured product. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.

In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
In the dropping method, first, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, liquid crystal microdrops are dropped into the sealing frame of the substrate in a state where the sealing agent is uncured, the other substrate is superposed under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Thereafter, heating is performed to perform main curing, and a liquid crystal display element is manufactured. At present, this dripping method has become the mainstream method for manufacturing liquid crystal display elements.

By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a technique for miniaturization, there is a narrow frame of the liquid crystal display unit, and for example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
With such a narrow frame design, in the liquid crystal display element, the distance from the pixel region to the sealing agent is close, and display unevenness due to contamination of the liquid crystal by the sealing agent is likely to occur.

In addition, with the spread of tablet devices and mobile devices, liquid crystal display elements are increasingly required to have moisture resistance reliability when driving in high-temperature and high-humidity environments, and the sealant prevents water from entering from the outside. There is a further demand for performance. In order to improve the moisture resistance reliability of the liquid crystal display element, in order to prevent water from entering from the interface between the sealing agent and the substrate, the adhesion of the sealing agent to the substrate, etc. is improved, and the moisture permeability of the sealing agent is prevented. It is necessary to improve the performance. As a method for improving the moisture permeation preventive property of the sealing agent, for example, a method of blending a filler such as talc can be considered. However, even when a filler such as talc is added in this way, when a strict moisture resistance reliability test is performed, there is a problem that display unevenness occurs in the liquid crystal display element.

JP 2001-133794 A International Publication No. 02/092718

An object of this invention is to provide the sealing compound for liquid crystal display elements which can make adhesiveness and moisture permeability prevention property of hardened | cured material compatible. Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element.

The present invention is a liquid crystal display element sealing agent containing a curable resin and a polymerization initiator and / or a thermosetting agent, and the curable resin contains a compound represented by the following formula (1). It is a sealing agent for liquid crystal display elements.

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a group represented by the following formula (2-1), (2-2), or (2-3) , Ar represents an optionally substituted arylene group, X represents a ring-opened structure of a cyclic lactone, n represents 0 or more and 5 or less (average value), and Ep represents a structure derived from an epoxy compound. To express.

In the formulas (2-1) to (2-3), * represents a bonding position. In the formula (2-2), a is an integer of 1 to 8, and in the formula (2-3) b is an integer of 1 to 8, c is an integer of 1 to 3, and d is an integer of 1 to 8.
The present invention is described in detail below.

The present inventor has surprisingly obtained a sealing agent for a liquid crystal display element that can achieve both adhesiveness and moisture permeation preventing property of a cured product by using a compound having a specific structure as a curable resin. As a result, the present invention has been completed.

The sealing agent for liquid crystal display elements of this invention contains curable resin.
The said curable resin contains the compound represented by the said Formula (1). By containing the compound represented by the above formula (1), the sealing agent for liquid crystal display elements of the present invention can achieve both adhesiveness and moisture permeation preventive property of the cured product.

The reason why the adhesiveness and the moisture permeation preventive property of the cured product can be made compatible by containing the compound represented by the above formula (1) is considered as follows.
Since the compound represented by the above formula (1) has a high proportion of aromatic rings in the molecule, it is considered that both the adhesion and the moisture permeation preventive property of the cured product are improved by the stacking effect. Moreover, since the side which has an epoxy group has a short distance from a center frame | skeleton to a reaction point, it contributes to the moisture-permeable prevention improvement of hardened | cured material. It is considered that the adhesiveness that tends to decrease when the distance from the central skeleton to the reaction point is short is improved by the fact that the reactive group is an epoxy group. Furthermore, the side having the (meth) acryloyl group is considered to contribute to the improvement of adhesion because the distance from the central skeleton to the reaction point is long.
In the present specification, the “(meth) acryloyl” means acryloyl or methacryloyl.

In the above formula (1), R ² represents a group represented by the above formula (2-1), (2-2), or (2-3). Among these, from the viewpoint of the adhesiveness of the obtained sealing agent for liquid crystal display elements and the flexibility of the cured product, R ² is preferably a group represented by the above formula (2-2). In 2-2), a group in which a is 2 (ethylene group) is more preferable.
In the above formulas (2-1) and (2-3), among the bond positions indicated by *, the bond position on the methylene group side is the bond position with the (meth) acryloyloxy group in the above formula (1). It becomes.

In said formula (1), Ar represents the arylene group which may be substituted.
Examples of the arylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, Examples include 2,6-naphthylene group and 2,7-naphthylene group. Of these, a 1,2-phenylene group and a 1,8-naphthylene group are preferable, and a 1,2-phenylene group is more preferable.

In the above formula (1), X represents a ring-opening structure of a cyclic lactone.
Examples of the cyclic lactone include γ-undecalactone, ε-caprolactone, γ-decalactone, σ-dodecalactone, γ-nonalactone, γ-nonanolactone, γ-valerolactone, σ-valerolactone, β-butyrolactone, γ -Butyrolactone, β-propiolactone, σ-hexanolactone, 7-butyl-2-oxepanone and the like. Among them, those in which the straight chain portion of the main skeleton has 5 to 7 carbon atoms when ring-opened are preferable.

In formula (1), Ep represents a structure derived from an epoxy compound.
Examples of the epoxy compound from which Ep is derived include, for example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol E type epoxy compounds, bisphenol S type epoxy compounds, resorcinol type epoxy compounds, dicyclopentadiene type epoxy compounds, and naphthalene. Type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, and the like.
Especially, as for the compound represented by the said Formula (1), it is preferable that Ep is a structure derived from a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, or a bisphenol E type epoxy compound.

The compound represented by the above formula (1) has excellent adhesion due to a high stacking effect even when n is 0 and moisture permeation prevention property of the cured product, and when n is 1 or more and 5 or less, Since the distance from the central skeleton having the (meth) acryloyl group to the reaction point can be increased, the balance between flexibility and rigidity is better.

Examples of the method for producing the compound represented by the above formula (1) include the following methods. That is, a step of reacting hydroxyalkyl (meth) acrylate with an aromatic carboxylic acid anhydride by heating and stirring in the presence of a polymerization inhibitor, and adding an epoxy compound to the obtained reaction product and heating and stirring. And a step of reacting a part of the epoxy groups of the epoxy compound.
Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
Examples of the aromatic carboxylic acid anhydride include phthalic anhydride and naphthalic anhydride.
Examples of the polymerization inhibitor include hydroquinone and p-methoxyphenol.
The hydroxyalkyl (meth) acrylate may be partially reacted with ε-caprolactone before reacting with the aromatic carboxylic acid anhydride.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate.

When manufactured by the above-described manufacturing method, the compound represented by the above formula (1) is obtained as a mixture of the compound represented by the following formula (3) and the raw material epoxy compound. That is, when using this mixture, in the sealing agent for liquid crystal display elements of the present invention, the curable resin contains a compound represented by the following formula (3).

In the formula (3), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a group represented by the following formula (4-1), (4-2), or (4-3) , Ar represents an optionally substituted arylene group, X represents a ring-opened structure of a cyclic lactone, m represents 0 or more and 5 or less (average value), and Ep represents a structure derived from an epoxy compound. To express.

In the formulas (4-1) to (4-3), * represents a bonding position, and in the formula (4-2), a is an integer of 1 to 8, and in the formula (4-3), b is an integer of 1 to 8, c is an integer of 1 to 3, and d is an integer of 1 to 8.

Incidentally, ^R 1 in the formula ^(3), R ^{2, Ar, X,} and, Ep ^{is, R} 1, ^R 2, Ar in formula (1), X, and, Ep and the respective like Become.
Also, in the above formulas (4-1) and (4-3), among the bond positions indicated by *, the bond position on the methylene group side is the bond position with the (meth) acryloyloxy group in formula (3). Become.

The preferable lower limit of the content of the compound represented by the formula (1) in 100 parts by weight of the curable resin is 1 part by weight, and the preferable upper limit is 35 parts by weight. When the content of the compound represented by the above formula (1) is within this range, the obtained sealing agent for liquid crystal display elements is more excellent in the effect of achieving both adhesiveness and moisture permeation prevention. The minimum with more preferable content of the compound represented by said Formula (1) is 5 weight part, and a more preferable upper limit is 25 weight part.

The sealing agent for liquid crystal display elements of the present invention may further contain other polymerizable compounds as the curable resin as long as the object of the present invention is not impaired.
The other polymerizable compound is a polymerizable compound other than the compound represented by the above formula (1), the compound represented by the above (3), and the epoxy compound that is a raw material of the above formula (1), Examples thereof include an epoxy compound (hereinafter also referred to as “other epoxy compound”), a (meth) acrylic compound (hereinafter also referred to as “other (meth) acrylic compound”), and the like.
In the present specification, the “(meth) acryl” means acryl or methacryl, and the “(meth) acryl compound” means a compound having a (meth) acryloyl group.

Examples of the other epoxy compounds include bisphenol A type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, and naphthalene. Type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, Examples include rubber-modified epoxy resins and glycidyl ester compounds.

Examples of commercially available bisphenol A type epoxy resins include jER828 and jER1001 (both manufactured by Mitsubishi Chemical Corporation).
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.

Moreover, the said curable resin may contain a partial (meth) acryl modified epoxy resin as said other epoxy compound.
In the present specification, the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and one or more (meth) acryloyl groups in one molecule. It can be obtained by reacting an epoxy group of a part of an epoxy compound having two or more epoxy groups therein with (meth) acrylic acid.

Examples of the other (meth) acrylic compounds include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable. The (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
In addition, in this specification, the said "epoxy (meth) acrylate" represents the compound which made all the epoxy groups in an epoxy compound react with (meth) acrylic acid.

Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, iso Myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Til (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 -Butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acrylic Examples include leuoxyethyl phosphate and glycidyl (meth) acrylate.

Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane. Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, poly Lopylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol Dicyclopentadienyl di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol Di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol (Meth) acrylate.

Further, among the above (meth) acrylic acid ester compounds, those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri ( (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.

As an epoxy compound used as a raw material for synthesize | combining the said epoxy (meth) acrylate, the thing similar to the other epoxy compound mentioned above can be used.

Examples of commercially available epoxy (meth) acrylates include, for example, an epoxy (meth) acrylate manufactured by Daicel Ornex, an epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., and an epoxy ( Examples include (meth) acrylate and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
The epoxy (meth) acrylate manufactured by the Daicel Orunekusu Inc., for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182, KRM8076, and the like.
Examples of the epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 and the like.
Examples of the epoxy (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 1600A, Epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA, and the like can be given.
Examples of the epoxy (meth) acrylate manufactured by Nagase ChemteX include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.

The urethane (meth) acrylate is obtained, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. be able to.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diene Isocyanate, 1,6,11-undecane triisocyanate and the like.

As the isocyanate compound, a chain-extended isocyanate compound obtained by a reaction between a polyol and an excess of an isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of divalent alcohol, mono (meth) acrylate or di (meth) acrylate of trivalent alcohol. And epoxy (meth) acrylate.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Can be mentioned.
Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
Examples of the trivalent alcohol include trimethylolethane, trimethylolpropane, and glycerin.
Examples of the epoxy (meth) acrylate include bisphenol A type epoxy acrylate.

Examples of commercially available urethane (meth) acrylates include, for example, urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Ornex, and urethane (meth) manufactured by Negami Kogyo Co., Ltd. Examples thereof include acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
Examples of the urethane (meth) acrylate manufactured by Toagosei include M-1100, M-1200, M-1210, and M-1600.
The urethane (meth) acrylate manufactured by the Daicel Orunekusu Inc., for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc. Can be mentioned.
Examples of the urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN- 7100, Art Resin UN-9000A, Art Resin UN-9000H, and the like.
Examples of the urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA- 4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, and the like.
Examples of the urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T. It is done.

The other (meth) acrylic compounds preferably have a hydrogen bonding unit such as —OH group, —NH— group, —NH ₂ group, etc. from the viewpoint of suppressing liquid crystal contamination.

The preferable lower limit of the content of the other polymerizable compound in 100 parts by weight of the curable resin is 5 parts by weight, and the preferable upper limit is 95 parts by weight. When the content of the other polymerizable compound is within this range, the obtained sealing agent for a liquid crystal display element is excellent in low liquid crystal contamination while maintaining excellent adhesiveness. The minimum with more preferable content of the said other polymeric compound is 10 weight part, and a more preferable upper limit is 90 weight part.

The sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.
Examples of the polymerization initiator include radical polymerization initiators and cationic polymerization initiators.

Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates radicals by heating, a photo radical polymerization initiator that generates radicals by light irradiation, and the like.

Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, and the like.

As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF, the radical photopolymerization initiator by Tokyo Chemical Industry, etc. are mentioned, for example.
Examples of the radical photopolymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucillin TPO.
Examples of the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat and having a number average molecular weight of 300 or more.

The preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo compound is within this range, it can be easily mixed with a curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).

Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable.
Specific examples of the polymer azo compound include, for example, a polycondensate of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group.
Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). .
Examples of commercially available azo compounds that are not polymers include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

As the cationic polymerization initiator, a photocationic polymerization initiator is preferably used.
The cationic photopolymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be of an ionic photoacid generation type or a nonionic photoacid generation type. It may be.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Is mentioned.

Examples of commercially available photocationic polymerization initiators include Adekaoptomer SP-150 and Adekaoptomer SP-170 (both manufactured by ADEKA).

The content of the polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination. The minimum with more preferable content of the said polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.

Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.

Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available solid organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Nippon Finechem Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., and the like.
Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Nippon Finechem Co., Ltd. include MDH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno Co. include Amicure VDH, Amicure VDH-J, Amicure UDH, and the like.

As for content of the said thermosetting agent, a preferable minimum is 1 weight part and a preferable upper limit is 50 weight part with respect to 100 weight part of whole curable resin. When the content of the thermosetting agent is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in curability while maintaining excellent coating properties and storage stability. The upper limit with more preferable content of the said thermosetting agent is 30 weight part.

The sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving the viscosity, further improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, improving the moisture resistance of the cured product, and the like. preferable.

As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.

The preferable lower limit of the content of the filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. When content of the said filler is this range, effects, such as an adhesive improvement, can be exhibited more, suppressing deterioration, such as applicability | paintability. The minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.

The sealing agent for liquid crystal display elements of the present invention preferably contains a silane coupling agent for the purpose of further improving the adhesiveness. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.

The minimum with preferable content of the said silane coupling agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness can be further exhibited while suppressing the occurrence of liquid crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.

The sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.

Titanium black is a substance having higher transmittance for light in the vicinity of the ultraviolet region, particularly for light with a wavelength of 370 nm to 450 nm, compared to the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. The light shielding agent contained in the liquid crystal display element sealant of the present invention is preferably a highly insulating material, and titanium black is also preferred as the highly insulating light shielding agent.

The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.

Examples of commercially available titanium black include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd.
Examples of the titanium black manufactured by Mitsubishi Materials include 12S, 13M, 13M-C, 13R-N, and 14M-C.
Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilac D.

The preferable lower limit of the specific surface area of the titanium black is 13 m ² / g, the preferable upper limit is 30 m ² / g, the more preferable lower limit is 15 m ² / g, and the more preferable upper limit is 25 m ² / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 μm. When the primary particle diameter of the light-shielding agent is within this range, the viscosity and thixotropy of the obtained sealing agent for liquid crystal display elements are not greatly increased, and the coating property is excellent. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light-shielding agent can be measured using a particle size distribution meter (for example, “NICOMP 380ZLS” manufactured by PARTICLE SIZING SYSTEMS).

The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, the effect of improving the light-shielding property is exhibited without lowering the adhesiveness, strength after curing, and drawing property of the obtained sealing agent for liquid crystal display elements. it can. The more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of the present invention is further added with a stress relaxation agent, reactive diluent, thixotropic agent, spacer, curing accelerator, antifoaming agent, leveling agent, polymerization inhibitor, etc., if necessary. An agent may be contained.

As a method for producing the sealing agent for liquid crystal display elements of the present invention, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin, and a polymerization Examples thereof include a method of mixing an initiator and / or a thermosetting agent and an additive such as a silane coupling agent added as necessary.

A vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention. The vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.

As the conductive fine particles, a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.

The liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.

The sealing agent for liquid crystal display elements of this invention can be used suitably for manufacture of the liquid crystal display element by a liquid crystal dropping method.
Examples of the method for producing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods.
First, a step of forming a rectangular seal pattern on the substrate by screen printing, dispenser application, or the like with the sealing agent for liquid crystal display elements of the present invention is performed. Next, the liquid crystal display element sealant or the like of the present invention is applied in an uncured state by applying liquid crystal microdroplets onto the entire surface of the transparent substrate and immediately stacking another substrate. Thereafter, a step of irradiating the seal pattern portion of the sealant for the liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily cure the sealant, and a step of heating and temporarily curing the temporarily cured sealant A liquid crystal display element can be obtained by performing the method.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which can make adhesiveness and moisture permeability prevention property of hardened | cured material compatible can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Preparation of curable resin mixture A)
To the reaction flask, 59 parts by weight of 2-hydroxyethyl methacrylate, 57 parts by weight of ε-caprolactone and 0.2 parts by weight of hydroquinone as a polymerization inhibitor were added and stirred at 90 ° C. for 5 hours using a mantle heater. 74 parts by weight of phthalic anhydride was added and further stirred for 5 hours. Next, 170 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, and the mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin mixture A.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin mixture A contains a compound represented by the above formula (1), a compound represented by the above formula (3), and bisphenol A diglycidyl ether, It was confirmed that the content ratio of the compound represented by the above formula (1) was 52% by weight. Further, the compound represented by the above formula (1) contained in the curable resin mixture A is a compound in which R ¹ is a methyl group, R ² is an ethylene group, Ar is a 1,2-phenylene group, and X is ε-caprolactone. It was confirmed that the ring structure, n was 1.01 (average value), and Ep was a structure derived from bisphenol A diglycidyl ether. Further, the compound represented by the above formula (3) contained in the curable resin mixture A is a compound in which R ¹ is a methyl group, R ² is an ethylene group, Ar is a 1,2-phenylene group, and X is ε-caprolactone. It was confirmed that the ring structure, m was 1.01 (average value), and Ep was a structure derived from bisphenol A diglycidyl ether.

(Preparation of curable resin mixture B)
In a reaction flask, 59 parts by weight of 2-hydroxyethyl methacrylate, 74 parts by weight of phthalic anhydride, and 0.2 parts by weight of p-methoxyphenol as a polymerization inhibitor are added, and stirred at 90 ° C. for 5 hours using a mantle heater. did. Next, 170 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, and the mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin mixture B.
^{According to 1} H-NMR and ¹³ C-NMR, the curable resin mixture B contains a compound represented by the above formula (1), a compound represented by the above formula (3), and bisphenol A diglycidyl ether, It was confirmed that the content ratio of the compound represented by the above formula (1) was 48% by weight. In addition, the compound represented by the above formula (1) contained in the curable resin mixture B is as follows: R ¹ is a methyl group, R ² is an ethylene group, Ar is a 1,2-phenylene group, n is 0, and Ep is bisphenol. It was confirmed that the structure was derived from A diglycidyl ether. Further, the compound represented by the above formula (3) contained in the curable resin mixture B is as follows: R ¹ is a methyl group, R ² is an ethylene group, Ar is a 1,2-phenylene group, m is 0, and Ep is bisphenol. It was confirmed that the structure was derived from A diglycidyl ether.

(Preparation of curable resin mixture C)
To the reaction flask, 59 parts by weight of 2-hydroxyethyl acrylate, 285 parts by weight of ε-caprolactone and 0.3 parts by weight of p-methoxyphenol as a polymerization inhibitor were added, and the mixture was stirred at 90 ° C. for 5 hours using a mantle heater. After that, 99 parts by weight of naphthalic anhydride was added and further stirred for 5 hours. Next, 170 parts by weight of bisphenol F diglycidyl ether was added to the obtained reaction product, and the mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin mixture C.
^{By 1} H-NMR and ¹³ C-NMR, the curable resin mixture C contains a compound represented by the above formula (1), a compound represented by the above formula (3), and bisphenol F diglycidyl ether, It was confirmed that the content ratio of the compound represented by the above formula (1) was 50% by weight. Further, the compound represented by the above formula (1) contained in the curable resin mixture C is a compound in which R ¹ is a hydrogen atom, R ² is an ethylene group, Ar is a 1,8-naphthylene group, and X is ε-caprolactone. It was confirmed that the ring structure, n was 4.98 (average value), and Ep was a structure derived from bisphenol F diglycidyl ether. Further, the compound represented by the above formula (3) contained in the curable resin mixture C is a compound in which R ¹ is a hydrogen atom, R ² is an ethylene group, Ar is a 1,8-naphthylene group, and X is ε-caprolactone. It was confirmed that the ring structure, m was 4.98 (average value), and Ep was a structure derived from bisphenol F diglycidyl ether.

(Preparation of curable resin mixture D)
To the reaction flask, 101 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate, 57 parts by weight of ε-caprolactone and 0.2 parts by weight of hydroquinone as a polymerization inhibitor were added, and the mixture was heated at 90 ° C. for 5 hours using a mantle heater. After stirring, 74 parts by weight of phthalic anhydride was added and further stirred for 5 hours. Next, 170 parts by weight of bisphenol A diglycidyl ether was added to the obtained reaction product, and the mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin mixture D.
^{According to 1} H-NMR and ¹³ C-NMR, the curable resin mixture D contains a compound represented by the above formula (1), a compound represented by the above formula (3), and bisphenol A diglycidyl ether, It was confirmed that the content ratio of the compound represented by the above formula (1) was 53% by weight. Further, in the compound represented by the above formula (1) contained in the curable resin mixture D, R ¹ is a hydrogen atom, R ² is a group represented by the above formula (2-1), Ar is 1,2- It was confirmed that the phenylene group, X was a ring-opened structure of ε-caprolactone, n was 1.00 (average value), and Ep was a structure derived from bisphenol A diglycidyl ether. Further, in the compound represented by the above formula (3) contained in the curable resin mixture D, R ¹ is a hydrogen atom, R ² is a group represented by the above formula (2-1), Ar is 1,2- It was confirmed that the phenylene group, X was a ring-opened structure of ε-caprolactone, m was 1.00 (average value), and Ep was a structure derived from bisphenol A diglycidyl ether.

(Production of propoxylated partially acrylic-modified bisphenol A type epoxy resin)
To the reaction flask, 58 parts by weight of 2-hydroxyethyl acrylate, 380 parts by weight of propylene oxide-modified bisphenol A diglycidyl ether, and 0.2 parts by weight of hydroquinone as a polymerization inhibitor were added, and the mixture was heated at 90 ° C. using a mantle heater. The mixture was stirred for a time to obtain a propoxylated partially acrylic modified bisphenol A type epoxy resin.
It was confirmed by ¹ H-NMR and ¹³ C-NMR that the obtained propoxylated partially acrylic-modified bisphenol A type epoxy resin had an epoxy equivalent of 385.

(Examples 1 to 7, Comparative Examples 1 and 2)
In accordance with the blending ratio described in Table 1, each material was stirred with a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), and then uniformly mixed with a ceramic three roll. To 7, Comparative Example 1 and 2 sealing agents for liquid crystal display elements were obtained.

<Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Table 1.

(Adhesiveness)
1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) was added to each of the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples, and two glass substrates with an ITO thin film (25 × 45 mm) was finely dropped. The other glass substrate with an ITO thin film was bonded to this in a cross shape, irradiated with 3000 mJ / cm ² ultraviolet rays with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to obtain an adhesive test piece. When the edge part of the board | substrate in the produced adhesion test piece was pushed in at a speed | rate of 5 mm / min using the metal cylinder with a radius of 5 mm, the intensity | strength in case panel peeling occurred was measured. The value obtained by dividing the obtained measured value (kgf) by the seal diameter (cm) was 3.0 kgf / cm or more, “◎”, 2.5 kgf / cm or more and less than 3.0 kgf / cm The case was evaluated as “◯” and the case where it was less than 2.5 kgf / cm was evaluated as “×”.

(Moisture permeability prevention)
Each sealing agent for liquid crystal display elements obtained in Examples and Comparative Examples was applied on a smooth release film so as to have a thickness of 200 μm or more and 300 μm or less using a coater. Subsequently, after irradiating 3000 mJ / cm < ² > of ultraviolet-rays using a metal halide lamp, the film for moisture permeability measurement was obtained by heating at 120 degreeC for 60 minutes. A moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture-proof packaging materials (cup method), the obtained moisture permeability measurement film was attached, and the temperature was 80 ° C. and humidity was 90% RH. The moisture permeability was measured by putting in a constant humidity oven. The case where the obtained moisture permeability value is less than 50 g / m ² · 24 hr is “◎”, and the case where it is 50 g / m ² · 24 hr or more and less than 60 g / m ² · 24 hr is “◯”, 60 g / m m ² · 24 hr or more ^{70 g} / m where the a was less than 2 · 24 hr or "△", was evaluated anti-moisture permeability as "×" the case was ^70g / m 2 · 24hr or more.

(Display performance of liquid crystal display elements)
In each of the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples, 1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) is blended, defoamed, After removing the foam, it was filled into a syringe for dispensing (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.), and defoamed again. Next, using a dispenser (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.), a sealing agent was applied so as to draw a frame on one of the two glass substrates with an ITO thin film. Subsequently, fine droplets of TN liquid crystal (manufactured by Chisso Corp., “JC-5001LA”) are dropped onto the sealant frame using a liquid crystal dropping device, and the other glass substrate with an ITO thin film is stacked on the vacuum bonding device. The two substrates were bonded together under a reduced pressure of 5 Pa. The cell after pasting was irradiated with 3000 mJ / cm ² ultraviolet rays with a metal halide lamp, and then the sealing agent was thermally cured by heating at 120 ° C. for 60 minutes, thereby producing a liquid crystal display element. The obtained liquid crystal display element was stored for 72 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then driven with a voltage of AC 3.5 V, and the presence or absence of display unevenness (color unevenness) was visually observed. “◎” indicates that no display unevenness is observed at the periphery of the liquid crystal display element, “○” indicates that display is slightly thin, and “△” indicates that there is clear dark display unevenness. The display performance of the liquid crystal display element was evaluated as “x” when the dark display unevenness was extended not only to the peripheral part but also to the central part.
Note that the liquid crystal display elements with the evaluations “◎” and “で” are at a level that causes no problem in practical use.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which can make adhesiveness and moisture permeability prevention property of hardened | cured material compatible can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.

Claims (6)

1. A sealing agent for a liquid crystal display element comprising a curable resin and a polymerization initiator and / or a thermosetting agent,
   The said curable resin contains the compound represented by following formula (1), The sealing compound for liquid crystal display elements characterized by the above-mentioned.
   

   

   In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a group represented by the following formula (2-1), (2-2), or (2-3) , Ar represents an optionally substituted arylene group, X represents a ring-opened structure of a cyclic lactone, n represents 0 or more and 5 or less (average value), and Ep represents a structure derived from an epoxy compound. To express.
   

   

   In the formulas (2-1) to (2-3), * represents a bonding position. In the formula (2-2), a is an integer of 1 to 8, and in the formula (2-3) b is an integer of 1 to 8, c is an integer of 1 to 3, and d is an integer of 1 to 8.
2. The sealing compound for liquid crystal display elements according to claim 1, wherein the compound represented by the formula (1) is contained in an amount of 1 to 35 parts by weight in 100 parts by weight of the curable resin.
3. The sealing agent for liquid crystal display elements according to claim 1 or 2, wherein the curable resin contains a compound represented by the following formula (3).
   

   

   In the formula (3), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a group represented by the following formula (4-1), (4-2), or (4-3) , Ar represents an optionally substituted arylene group, X represents a ring-opened structure of a cyclic lactone, m represents 0 or more and 5 or less (average value), and Ep represents a structure derived from an epoxy compound. To express.
   

   

   In the formulas (4-1) to (4-3), * represents a bonding position, and in the formula (4-2), a is an integer of 1 to 8, and in the formula (4-3), b is an integer of 1 to 8, c is an integer of 1 to 3, and d is an integer of 1 to 8.
4. The sealing agent for liquid crystal display elements according to claim 1, 2 or 3, further comprising a light shielding agent.
5. A vertical conduction material comprising the sealing agent for liquid crystal display elements according to claim 1, and conductive fine particles.
6. A liquid crystal display element comprising the sealant for a liquid crystal display element according to claim 1, 2, 3, or 4, or the vertical conduction material according to claim 5.